US3578843A - Control of light reflected from a mirror - Google Patents

Control of light reflected from a mirror Download PDF

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US3578843A
US3578843A US773690A US3578843DA US3578843A US 3578843 A US3578843 A US 3578843A US 773690 A US773690 A US 773690A US 3578843D A US3578843D A US 3578843DA US 3578843 A US3578843 A US 3578843A
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electrodes
layer
persistent
electrochromic
materials
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US773690A
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George Augustus Castellion
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Wyeth Holdings LLC
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American Cyanamid Co
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1524—Transition metal compounds

Definitions

  • electrochromic device being a andwich 350/290 arrangement of a pair of transparent electrodes, and a film of a ll!- Cl, transition metal compound and an insulating disposed Fleld of Search between the electrodes
  • the electrochromic device [56] References Cited coloration and bleaching thereof at ambient temperature by control of the polarity of an applied electric field, whereby UNITED STATES PATENTS light reaching the reflecting layer is modulated in intensity, 3,453,038 7/1969 Kissa et al 350/160 thus modulating, in turn, the reflected light.
  • electro-optical devices exhibiting a phenomenon known as persistent electrochromism.
  • This term denotes the property of a material whereby its electromagnetic radiation absorption characteristic is altered, in most instances even at ambient temperature, under the influence of an electric field.
  • Such materials may exhibit little or no absorption of visible wavelengths in the absence of an electric field and therefore be transparent, but when subjected to an electric field, effectively absorb in the red end of the spectrum, turning blue in color. Similar effects can be observed in other portions of the electromagnetic radiation spectrum, invisible as well as visible.
  • the radiation transmitting characteristic of the material will change. If the electrodes and the electrochromic layer are formed on the surface of a transparent substrate, such as glass, the light transmitting characteristics of the combination can be varied by controlling the electric field produced across the electrochromic layer. Thus, if the sandwich" of electrodes and electrochromic material on the substrate originally is clear, i.e.
  • An additional layer is placed between one of the electrodes and the electrochromic material, the additional layer being of a material which can be characterized as a current carrier permeable insulator. It has been found that when such a material is added to the prior device, not only does it permit the absorption characteristic of the electrochromic material to change rapidly under the influence of an electric field of a given polarity, even at ambient temperature, but it also renders the electrochromic layer sensitive to a field of the opposite polarity to return it positively to the absorption characteristic state it occupied prior to the initial application of the field, at a rate dependent upon the magnitude of the reverse field. In certain cases, the return to initial state may be effected at a relatively slow rate simply by providing a highly conductive, e.g., short circuit, path between the two electrodes.
  • the prior device had utility as a device for controlling transmitted light, that is light passing through the device.
  • the device would serve as an additional element in an optical system incorporating reflection elements.
  • Another object is to provide a light reflecting device having electro-optical light modulating means.
  • a further object is to provide a light reflecting device having infinitely variable light modulation ability.
  • the device of the invention comprises in sandwich arrangement, a first transparent electrode, a current carrier permeable insulator, a persistent electrochromic layer, a second elec' trode, a transparent support, and a reflecting layer.
  • the electrochromic layer will color, thus the amount of light reaching the reflecting surface from the side of the first electrode and being reflected back will be reduced. Reversing the circuit polarity will cause the electrochromic layer to bleach to the colorless state, thus increasing the reflected light from the reflecting surface to the normal intensity.
  • FIGS. 2 and 3 are diagrammatic illustrations of the inventive device in the modulation of reflected radiation.
  • FIG. 4 illustrates, in partial cross section, an alternative device according to the invention.
  • a persistent electrochromic material is defined as a material responsive to the application of an electric field of a given polarity to change from a first persistent state in which it is essentially nonabsorptive of electromagnetic radiation in a given wavelength region to a second persistent state in which it is absorptive of electromagnetic radiation in the given wavelength region, and once in said second state, responsive to the application of an electric field of the opposite polarity to return to its first state.
  • Certain of such materials can also be responsive to a short circuiting condition, in the absence of an electric field, so as to return to the initial state.
  • persistent means the ability of the material to remain in the absorptive state to which it is changed, after removal of the electric field, as distinguished from a substantially instantaneous reversion to the initial state, as in the case of the Franz-Keldysh effect.
  • the materials which form the electrochromic materials of the device in general are electrical insulators or semiconductors. Thus are excluded those metals, metal alloys, and other metal-containing compounds which are relatively good electrical conductors.
  • the materials contain in nonstoichiometric proportions at least two different elements, said elements being present as ions of opposite polarity.
  • This condition produces lattice defects as distinguished from mere physical displacement of crystal symmetry, although the condition may also result in or be evidenced by such.
  • Lattice vacancies are particular instances of lattice defects as, for example, an oxygen vacancy in a metal oxide crystal.
  • the first and preferred class (I) comprises materials disclosed in the above-mentioned prior patent applications. These materials exhibit persistent electrochromism over a wide temperature range including ambient temperature and in some instances high temperatures, e.g,, above about C. or low temperatures, e.g., below about -50 C.
  • ambient temperature is meant temperatures normally encountered in the fields of use of the devices such as described hereinafter, e.g., ---50C to 125 C.
  • the second class (ll) comprises materials which exhibit persistent electrochromism only at relatively high (nonambient) temperature, e.g., above about 125 C.
  • these materials are gross crystals or crystalline layers or films of alkali halides such as NaCl, RbCl, KCl, LiF, NaBr, KBr, Kl, RbBr, and the like, as described in-British Pat. No. 845,053 and corresponding West German Pat. 1,036,388.
  • Combinations of class (I) and class (ll) materials may also be employed.
  • the class (1) materials are further characterized as inorganic substances which are solid under the conditions of use, whether as pure elements. alloys, or chemical compounds, containing at least one element of variable oxidation state, that is, at least one element of the Periodic System which can exist in more than one oxidation state in addition to zero.
  • oxidation state as employed herein is defined in "Inorganic Chemistry," T. Moeller, John Wiley & Sons, lnc., New York, 1952. These include materials containing a transition metal element (including Lanthanide and Actinide series elements); materials containing nonalkali metal elements such as copper, tin and barium; and materials containing an alkali metal element with a variable oxidation state element.
  • Preferred materials of this class are films of transition metal compounds in which the transition metal may exist in any oxidation state from +2 to +8. Examples of these are: transition metal oxides, transition metal sulfides, transition metal oxysulfides, transition metal halides, selenides, tellurides, chromates, molybdates, tungstates, vanadates, niobates, tantalates, titanates, stannates, and the like. Particularly preferred are films of metal stannates, oxides and sulfides of the metals of Groups IVB, VB and VIB of the Periodic System. and Lanthanide series metal oxides and sulfides.
  • Examples of such are copper stannate, tungsten oxide, molybdenum oxide, titanium oxide, vanadium oxide, niobium oxide, cerium oxide, cobalt tungstate, metal molybdates, metal titanates, metal niobates, and the like.
  • the class (I) electrochromic materials are distinguished from prior known organic or inorganic materials which exhibit coloration in an electric field as a result of the Franz-Kcldysh effect or the effect Platt describes as electrochromism.
  • Platt See J. Chem. Phys. 34, 8623 (I961). ln the latter cases, coloration results from the shifting of an existing absorption band or spectral line by the electric field; whereas in the present invention, upon coloration, an absorption band is created where none existed before, or removed bleaching.
  • thickness desirably will be in the range of from about 0.l--l microns.
  • 0. lmicrons are preferred over thicker ones.
  • Optimum thickness will also be determined by the nature of the particular compounds being laid down as films and by the film-forming method since the particular compound and filmforming method may place physical (e.g., nonuniform film surface) and economic limitations on manufacture of the devices.
  • the films may be self-supporting, depending on thickness and film material, or may be laid down on any substrate which, relative to the film, is electrically nonconducting.
  • Suitable substrate materials include glass, wood, paper, plastics. and the like, including transparent, translucent, opaque or other optical quality materials.
  • the preferred electrochromic material for use with the insulating layer is a class (1) material as defined above.
  • class (ll) electrochromic materials is also improved since the electrochromic material is made polarity sensitive thereby, that is, responsive to a field of one polarity but not to both at the same time as in the prior art device of British Patent 845,053.
  • FIG. 1 illustrates a device in accordance with the invention.
  • a substrate 22 such as glass or other transparent material
  • a persistent electrochromic material 26 an insulating material 27 and a second conductive material 28, and a reflecting layer 29 on the opposite side of substrate 22.
  • the conductive materials are of optical quality effective for passing light to reflecting layer 29.
  • the substrate 22 and the conductive layer 24 may conveniently be provided as a unit by so-called NESA" glass, a commercially available product having a transparent coating of conductive tin oxide on one surface of a glass sheet.
  • the layers 26 and 28 may then be deposited on the tin oxide layer known vacuum deposition techniques.
  • the persistent electrochromic material may be tungsten oxide or molybdenum oxide, for example the outer electrode 28 may be a gold film.
  • a source of DC potential 30 is coupled between the conductive films with its positive terminal on the tin oxide layer and its negative terminal on the gold outer layer.
  • the insulating layer 27 may be defined as a current carrier permeable insulator and as used herein is intended to denote any material of electrical resistivity sufficient to provide continuous effective insulation against normal electrical conduction between opposed surfaces of the electrodes.
  • Numerous well-known materials are suitable for use as current carrier permeable insulators in this invention. These include an air gap or vacuum gap; normally substantially nonconductive substances such as plastics, e.g., polyesters, vinyl or like polymers, allylic or like polymers, polycarbonates, phenolics, amino resins, polyamides, polyinides, cellulosic resins, and others whether solvent or water soluble or insoluble.
  • metal oxides or sulfides prepared by oxidizing or sulfidizing a metal electrode surface such that the insulator is formed directly on the electrode.
  • An example is the combination of an aluminum electrode and aluminum oxide insulator coating.
  • Other such inorganic insulators contemplated are selenide, arsenide, nitride, chloride, fluoride, bromide and carbide films.
  • the insulator may be a fluid (liquid or gas), low melting solid, or solid or liquid mixture of two or more different insulating materials.
  • Three suitable insulators are silicon oxide, calcium fluoride and magnesium fluoride.
  • the insulator is a film of at least about 0.00] microns thickness, for example, in the range of about 0.001- 1.0 microns.
  • the mechanism by which the current carrier permeable insulaior improves the performance of the persistent electrochromic material can be understood as a selective introduction of charge carriers (i.e., electrons, holes, positive or negative ions) suitable for the subsequent production of persistent coloration in the electrochromic material.
  • the current carrier permeable insulator thereby renders the electrochromic material polarity sensitive, with the result that application of a voltage of polarity opposite that which produces coloration will result in bleaching without simultaneous recoloration.
  • This general mechanism may be viewed more particularly as two cases or theories, electronic and ionic. Each case explains certain observations not adequately explained by the other case, and it is not altogether implausible that the mechanisms may operate simultaneously although independently.
  • the current carrier permeable insulator functions by nonclassical transposition (tunneling) of electrons or holes through the energy barrier junction between the insulator and the persistent electrochromic material.
  • An equivalent characterization of such insulator materials in this view is that they exhibit an energy gap between their valence and conduction bands of width sufficient at the temperature of use to impede normal electrical conduction through the material of the insulator but nevertheless, because of their thinness, permit quantum mechanical tunneling of current carriers, i.e., electrons or holes.
  • the current carriers which are injected by the tunneling process through the insulator into the persistent electrochromic material possess sufiicient energy to become trapped in the energy level sites which produce the color centers observed as the coloration of the persistent electrochromic material.
  • the current carrier permeable insulator can serve to block entirely the passage of an electronic current (i.e., electrons or holes) but permit the transfer through it of ions.
  • the insulator serves to facilitate the production of color centers in the persistent electrochromic layer by providing a large electric field gradient through which ions may move rapidly, even at ambient temperature, to be removed or added to the persistent electrochromic material.
  • the insulator layer can also serve as a temporary or permanent repository for ions removed from the electrochromic layer.
  • the reflective layer 29 is applied to the opposite side of substrate 22 and may be any known material which will reflect light such as silver, aluminum, mercury alloys and the like, which are widely used for mirror surfaces.
  • the device functions effectively in a reversible manner.
  • the battery 30 is coupled to the electrodes 24 and 28 through a reversing switch indicated generally at 36.
  • the switch arm in the position to produce coloration, the positive terminal of the source is connected to the outer or gold electrode while the negative terminal is connected to the tin oxide layer on the glass substrate.
  • the switch 36 may be opened, disconnecting the battery from the device entirely, and the device will remain in its darkened state without further application of power.
  • the switch arm is thrown to the bleach" contacts, across which is connected a potentiometer 37.
  • the potentiometer contact or slider is movable from a point at which the electrodes 24 and 28 are short circuited to a point at which full battery voltage, of polarity opposite to the coloration condition, is applied between them. Any number of reverse voltage values may be obtained between the two extremes.
  • a bleach" voltage of a value less than battery voltage is applied across the electrodes, setting up a corresponding electric field. Under the influence of this field, the device returns to its initial uncolored state.
  • the rapidity with which the bleaching occurs is determined by the magnitude of the voltage; the higher the voltage; the faster the bleaching process is completed. At the higher bleaching voltages, it has been found that the bleaching process .is even faster than the coloring operation. Once the bleaching is completed, no further coloration is observed with this polarity and the switch may be opened to disconnect the battery from the device and minimize power drain.
  • the device of FIG. 1 functions as a self-contained modulator for reflected light.
  • a light ray 40 is reflected as a substantially full intensity ray 42 when the device 20 is in a bleached state.
  • the amount of light from ray 40 passing through the colored electrochromic layer 26 to the reflecting layer 29 and from the reflecting layer is less due to absorption.
  • the reflected ray 41A is lower in intensity.
  • the difference in intensity may be varied as desired by controlling the density of coloration of electrochromic layer 26.
  • the coloration is a function of the time that the current is applied, up to a certain maximum coloration.
  • the current is applied for any time interval less than that required to obtain maximum coloration, a lesser amount of coloration will be obtained which will absorb less light, giving more reflected light.
  • the amount of reflected light may thus be varied from the total, to any amount down to the minimum allowed.
  • ELECTRODES Virtually any material exhibiting electrical conductivity may be used for an electrode. The same material may be used for both electrodes or each electrode may be of a different material, or mixture or alloys of different materials. Typical electrode materials are the metals, e.g., gold, silver, aluminum, and conducting nonmetals such as carbon, suitable doped tin or indium oxide, and the like. As already indicated, at at least one of the electrodes should be of an optical quality effective for transmission of the electrochromic change, if in the visible, or for instrumentally sensing the change, if not in the visible range.
  • the negative and positive electrodes need only be in electrical contact with the film. Any type and arrangement of electrodes and film effective to impose an electric field on the film when the electrodes are connected to a voltage source, will be suitable.
  • the electrodes may be spaced conducting strips deposited on or imbedded in the film, or they may be conducting layers between which the film is inserted.
  • class (I) electrochromic materials may be employed in accordance with the present invention. While the following examples describe devices incorporating class (I) electrochromic materials, it should be'junderstood that where high temperature use is contemplated, class (II) electrochromic materials may be employed.
  • Example 1 A film of molybdenum oxide, about 1.0 micron in thickness, is thermally evaporated by conventional means at a pressure of 10 Torr. from an electrically heated tantalum boat onto the tin oxide coated side of NESA" glass, the tin oxide on the glass forming the first electrode. A layer of silver was deposited on the opposite layer of the NESA" glass. A very thin film of silicon oxide (about 200 angstroms thick) an insulating material, is then deposited in like manner onto the molybdenum oxide layer. Finally, a thin film of gold (about lOO angstroms thick) effectively transparent, is deposited over the silicon oxide insulating layer to form the second electrode of the layered structure or sandwich.
  • the molybdenum oxide film When an electric field of from to 7 volts is applied across the foregoing sandwich structure with the gold layer as the positive electrode and the tin oxide as the negative electrode, the molybdenum oxide film, normally colorless, is colored blue uniformly over the entire surface, reducing the reflected light transmission of the device to about percent in 30 seconds. The coloration remains substantially permanent when the electric field is removed.
  • Example 2 The device is fabricated as described in connection with Example 1 except that a film of tungsten oxide is substituted for the molybdenum oxide.
  • Table I illustrates other combinations of persistent electrochromic materials and insulating materials which when supported as films between electrode materials substantially as described in Examples 1 and 2 exhibit the reflected radiation transmission characteristics of the invention.
  • FIG. 4 a variatlon of the device is shown wherein the glass substrate 22, reflecting layer 29, and conductor 24 are replaced by a single reflecting layer 25.
  • the single layer serves as both the conductor and the reflector by connecting the electric current carrier thereto.
  • the device of FIG. 1 could also be modified by replacing conductor 24 with a conductive, reflective material and omitting layer 29.
  • the inventive device can be useful in many ways. It can be used as part of an optical system involving reflective elements where close control of light intensity is desired without modifying its other properties. Thus no diaphragms or other separate light modulating elements would be necessary. Moreover, the optics may be simpler since the light rays are not altered except in intensity.
  • the device has been illustrated as having a flat reflecting surface, it will be obvious that the reflecting surface may take any desired configuration such as a spherical or parabolic surface, for example.
  • the device is particularly suitable as a rear view mirror in motor vehicles for night driving. It is possible by the use of the device to reduce the intensity of reflected light from headlights of a following vehicle to a desired degree by merely coloring the electrochromic layer. This can be done by mere switching and is thus quick and effective.
  • a radiation reflecting device having an electric field responsive radiation transmitting characteristic comprising in sandwich layer arrangement, a pair of electrodes, a layer of a persistent electrochromic material of about 0.01 to microns thickness in contact with one of said electrodes, layer of an insulating material of about 0.001 to 1.0 microns thickness in contact with both said electrochromic material and the other of said electrodes, and a layer of reflecting material.
  • said insulating material is silicon monoxide, calcium fluoride or magnesium fluoride and said persistent electrochromic material is a metal stannate, a Group IVB, VB or VIB metal oxide, or a Lanthanide series metal oxide.
  • a variable light transmitting system as in claim 1 comprising a device having a pair of conductive electrodes; a persistent electrochromic material and an insulating material disposed between said electrodes, and a reflective layer on one of said electrodes, and a control means coupled to said electrodes for selectively applying across said electrodes a potential of one polarity; a potential of the opposite polarity; or an effective short circuit.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nonlinear Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Optical Elements Other Than Lenses (AREA)
US773690A 1968-09-25 1968-09-25 Control of light reflected from a mirror Expired - Lifetime US3578843A (en)

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US3704057A (en) * 1971-06-02 1972-11-28 American Cyanamid Co Electrochromic device having identical display and counter electrode materials
US3712710A (en) * 1970-12-21 1973-01-23 American Cyanamid Co Solid state electrochromic mirror
US3807832A (en) * 1972-11-09 1974-04-30 American Cyanamid Co Electrochromic (ec) mirror which rapidly changes reflectivity
DE2361114A1 (de) * 1972-12-13 1974-06-20 American Cyanamid Co Strahlungsreflektor
US3827784A (en) * 1971-12-09 1974-08-06 American Cyanamid Co Simple, bonded graphite counter electrode for electrochromic devices
US3836229A (en) * 1972-01-12 1974-09-17 Ebauches Sa Electro-optical display device
US3847468A (en) * 1972-12-07 1974-11-12 American Cyanamid Co Ammonia-treated electrochromic (ec) electrodes
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US3892472A (en) * 1973-12-26 1975-07-01 American Cyanamid Co Self-supporting pigment layers for electrochromic display
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US4277147A (en) * 1979-01-15 1981-07-07 General Motors Corporation Display device having reduced electrochromic film dissolution
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US4865428A (en) * 1987-08-21 1989-09-12 Corrigan Dennis A Electrooptical device
US4902108A (en) * 1986-03-31 1990-02-20 Gentex Corporation Single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof
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US5122647A (en) * 1990-08-10 1992-06-16 Donnelly Corporation Vehicular mirror system with remotely actuated continuously variable reflectance mirrors
US5138481A (en) * 1991-07-23 1992-08-11 Ford Motor Company Electrochromic device with color gradient and method of making the device
US5148014A (en) * 1990-08-10 1992-09-15 Donnelly Corporation Mirror system with remotely actuated continuously variable reflectant mirrors
US5202787A (en) * 1992-01-10 1993-04-13 Gentex Corporation Electro-optic device
US5240646A (en) * 1990-06-11 1993-08-31 Centre National De La Recherche Scientifique Electrochromic materials
US5724177A (en) * 1991-09-04 1998-03-03 Sun Active Glass Electrochromics, Inc. Electrochromic devices and methods
US6055088A (en) * 1996-08-22 2000-04-25 Saint-Gobain Vitrage Glazing with variable optical and/or energetic properties
US6185034B1 (en) * 1998-11-20 2001-02-06 Murakami Corporation Electrochromic device
WO2008037692A1 (de) * 2006-09-28 2008-04-03 Siemens Aktiengesellschaft Vorrichtung mit zwei elektroden und einer zwischen den elektroden befindlichen elektrochromen schicht, verfahren zum betreiben der vorrichtung sowie verwendung der vorrichtung
US20090231738A1 (en) * 2008-03-11 2009-09-17 Us Government As Represented By Secretary Of The Army Mirrors and methods of making same
US20130222812A1 (en) * 2009-12-04 2013-08-29 Crystalvue Medical Corporation Optical coherence tomography apparatus and operating method thereof
US9782949B2 (en) 2008-05-30 2017-10-10 Corning Incorporated Glass laminated articles and layered articles
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US20240210779A1 (en) * 2021-06-10 2024-06-27 Zhejiang University Inorganic multi-color transmission electrochromic films, electrochromic coated glass electrodes and the design method

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JPS62196121U (enrdf_load_html_response) * 1986-05-30 1987-12-14
KR102670716B1 (ko) * 2021-08-19 2024-05-29 삼성중공업 주식회사 모듈형 거주구

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US3462712A (en) * 1966-11-23 1969-08-19 Bell Telephone Labor Inc Optical modulator

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US3712710A (en) * 1970-12-21 1973-01-23 American Cyanamid Co Solid state electrochromic mirror
US3704057A (en) * 1971-06-02 1972-11-28 American Cyanamid Co Electrochromic device having identical display and counter electrode materials
US3827784A (en) * 1971-12-09 1974-08-06 American Cyanamid Co Simple, bonded graphite counter electrode for electrochromic devices
US3836229A (en) * 1972-01-12 1974-09-17 Ebauches Sa Electro-optical display device
US3807832A (en) * 1972-11-09 1974-04-30 American Cyanamid Co Electrochromic (ec) mirror which rapidly changes reflectivity
US3847468A (en) * 1972-12-07 1974-11-12 American Cyanamid Co Ammonia-treated electrochromic (ec) electrodes
US3844636A (en) * 1972-12-13 1974-10-29 American Cyanamid Co Electrochromic mirror
DE2361114A1 (de) * 1972-12-13 1974-06-20 American Cyanamid Co Strahlungsreflektor
DE2446241A1 (de) * 1973-09-29 1975-04-10 Matsushita Electric Ind Co Ltd Farbwiedergabevorrichtung
US3963314A (en) * 1973-09-29 1976-06-15 Matsushita Electric Industrial Co., Ltd. Color display device
USRE30835E (en) * 1973-12-26 1981-12-29 American Cyanamid Company Self-supporting pigment layers for electrochromic display
US3892472A (en) * 1973-12-26 1975-07-01 American Cyanamid Co Self-supporting pigment layers for electrochromic display
US3995940A (en) * 1974-03-12 1976-12-07 Commissariat A L'energie Atomique Luminous display device
US4034550A (en) * 1975-04-08 1977-07-12 Kabushiki Kaisha Suwa Seikosha Electronic wristwatch digital display
DE2629874A1 (de) * 1975-07-02 1977-01-27 Citizen Watch Co Ltd Erregerstromkreis fuer eine elektrochromatische anzeige und verfahren zum erregen ihrer anzeigesegmente
US4251138A (en) * 1975-12-22 1981-02-17 Lusis Andrei R Method of producing solid electrochrome element
DE2739613A1 (de) * 1976-09-03 1978-03-23 Sharp Kk Verfahren zum aussteuern einer elektrochromatischen anzeigevorrichtung und elektrochromatischen anzeigevorrichtung hierfuer
US4256372A (en) * 1977-10-03 1981-03-17 Minolta Camera Kabushiki Kaisha Catadioptric lens system with light transmission control means
US4146309A (en) * 1978-03-10 1979-03-27 Bell Telephone Laboratories, Incorporated Process for producing evaporated gold films
US4372653A (en) * 1978-12-12 1983-02-08 Wert Iii John C Polarizing beam splitting phase transition optical modulator
US4277147A (en) * 1979-01-15 1981-07-07 General Motors Corporation Display device having reduced electrochromic film dissolution
US4465339A (en) * 1980-03-07 1984-08-14 Jenaer Glaswerk Schott & Gen. Electrochromic mirrors
US4500174A (en) * 1983-01-05 1985-02-19 Conner Bruce E Electrochromic imaging apparatus
US4804275A (en) * 1985-08-29 1989-02-14 Johnson Matthey Public Limited Company Indicator device for indicating the time integral of a monitored parameter
US4902108A (en) * 1986-03-31 1990-02-20 Gentex Corporation Single-compartment, self-erasing, solution-phase electrochromic devices, solutions for use therein, and uses thereof
AU586547B2 (en) * 1986-04-02 1989-07-13 Donnelly Corporation Electrochromic mirror
EP0241217A1 (en) * 1986-04-02 1987-10-14 Donnelly Corporation Electrochromic mirror
US4712879A (en) * 1986-04-02 1987-12-15 Donnelly Corporation Electrochromic mirror
US4865428A (en) * 1987-08-21 1989-09-12 Corrigan Dennis A Electrooptical device
EP0363045A1 (en) * 1988-10-05 1990-04-11 Ford Motor Company Limited Electrochromic devices having a gradient of colour intensities
US4923289A (en) * 1988-10-05 1990-05-08 Ford Motor Company Electrochromic devices having a gradient of color intensities
US5240646A (en) * 1990-06-11 1993-08-31 Centre National De La Recherche Scientifique Electrochromic materials
US5122647A (en) * 1990-08-10 1992-06-16 Donnelly Corporation Vehicular mirror system with remotely actuated continuously variable reflectance mirrors
US5148014A (en) * 1990-08-10 1992-09-15 Donnelly Corporation Mirror system with remotely actuated continuously variable reflectant mirrors
US5138481A (en) * 1991-07-23 1992-08-11 Ford Motor Company Electrochromic device with color gradient and method of making the device
WO1993002382A1 (en) * 1991-07-23 1993-02-04 Ford Motor Company Limited Electrochromic device with colour gradient and method of making the device
US5757537A (en) * 1991-09-04 1998-05-26 Sun Active Glass Electrochromics, Inc. Electrochromic devices and methods
US5724177A (en) * 1991-09-04 1998-03-03 Sun Active Glass Electrochromics, Inc. Electrochromic devices and methods
US5202787A (en) * 1992-01-10 1993-04-13 Gentex Corporation Electro-optic device
US6055088A (en) * 1996-08-22 2000-04-25 Saint-Gobain Vitrage Glazing with variable optical and/or energetic properties
US6185034B1 (en) * 1998-11-20 2001-02-06 Murakami Corporation Electrochromic device
WO2008037692A1 (de) * 2006-09-28 2008-04-03 Siemens Aktiengesellschaft Vorrichtung mit zwei elektroden und einer zwischen den elektroden befindlichen elektrochromen schicht, verfahren zum betreiben der vorrichtung sowie verwendung der vorrichtung
US8371705B2 (en) * 2008-03-11 2013-02-12 The United States Of America As Represented By The Secretary Of The Army Mirrors and methods of making same
US20090231738A1 (en) * 2008-03-11 2009-09-17 Us Government As Represented By Secretary Of The Army Mirrors and methods of making same
US9782949B2 (en) 2008-05-30 2017-10-10 Corning Incorporated Glass laminated articles and layered articles
US20130222812A1 (en) * 2009-12-04 2013-08-29 Crystalvue Medical Corporation Optical coherence tomography apparatus and operating method thereof
US8755050B2 (en) * 2009-12-04 2014-06-17 Crystalvue Medical Corporation Optical coherence tomography apparatus and operating method thereof
WO2018152250A1 (en) * 2017-02-14 2018-08-23 Nitto Denko Corporation Electrochromic devices
WO2020041632A1 (en) * 2018-08-23 2020-02-27 Nitto Denko Corporation Ultrathin electrochromic device for high optical modulation
CN112771443A (zh) * 2018-08-23 2021-05-07 日东电工株式会社 用于高光学调制的超薄电致变色设备
JP2021534466A (ja) * 2018-08-23 2021-12-09 日東電工株式会社 高光変調用極薄型エレクトロクロミックデバイス
US20240210779A1 (en) * 2021-06-10 2024-06-27 Zhejiang University Inorganic multi-color transmission electrochromic films, electrochromic coated glass electrodes and the design method

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CA943221A (en) 1974-03-05
SE379592B (enrdf_load_html_response) 1975-10-13
GB1248838A (en) 1971-10-06
FR2041020A6 (enrdf_load_html_response) 1971-01-29
HK30276A (en) 1976-05-28
JPS577418B1 (enrdf_load_html_response) 1982-02-10
DE1948362B2 (de) 1978-04-27
DE1948362C3 (de) 1980-10-16
DE1948362A1 (de) 1970-07-23

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